Palladium Complexes with the Tripodal Phosphine Tris(2-diphenylphosphinoethyl)amine. Synthesis and Structure of Trigonal, Tetrahedral, Trigonal Bipyramidal, and Square Planar Complexes

DOI: 10.1039/DT9890000211

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 211 - 216 (1989)

Update date:2022-07-29

Topics:

Authors:

Cecconi, Franco

Ghilardi, Carlo A.

Midollini, Stefano

Moneti, Simonetta

Orlandini, Annabella

Scapacci, Giancarlo

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Article abstract of DOI:10.1039/DT9890000211

The tripod-like ligand N(CH2CH2PPh2)3 (tdpea) forms the palladium(0) trigonal complex *0.5Me2CO, (1), in which the apical nitrogen atom of the phosphine is unco-ordinated.This unsaturated species undergoes both addition (CO, SO2) and oxidative-addition reactions (alkyl halides) to form respectively tetrahedral and trigonal bipyramidal complexes.The latter contain quadridentate tdpea.Complex (1) reacts with CO2 or CS2 in the presence of O2 to form a square planar carbonate or dithiocarbonate derivative, with oxidation of a terminal PPh2 group to OPPh2.Crystal data for (1) are: a=10.827(8) Angstroem, α=108.82(9) deg, space group R3, and Z=1.In the molecule the metal atom displays an unprecedented out-of-plane trigonal co-ordination.Crystal data for I are: a=10.570(7) Angstroem, α=106.10(7) deg, space group R3, and Z=1.The geometry of the (1+) cation is trigonal bipyramidal, with the three-fold crystallographic axis passing through the nitrogen, the palladium, and the carbon atom.